1. Field of the Invention
This invention relates to the fluidized catalytic cracking (FCC) conversion of heavy hydrocarbons into lighter hydrocarbons with a fluidized stream of catalyst particles and regeneration of the catalyst particles to remove coke which acts to deactivate the catalyst. More specifically, this invention relates to the reduction of sulfur oxide emissions from the flue gas of an FCC process.
2. Description of the Prior Art
Catalytic cracking is accomplished by contacting hydrocarbons in a reaction zone with a catalyst composed of finely divided particulate material. The reaction in catalytic cracking, as opposed to hydrocracking, is carried out in the absence of added hydrogen or the consumption of hydrogen. As the cracking reaction proceeds, substantial amounts of coke are deposited on the catalyst. A high temperature regeneration within a regeneration zone operation burns coke from the catalyst. Coke-containing catalyst, referred to herein as spent catalyst, is continually removed from the reaction zone and replaced by essentially coke-free catalyst from the regeneration zone. Fluidization of the catalyst particles by various gaseous streams allows the transport of catalyst between the reaction zone and regeneration zone. Methods for cracking hydrocarbons in a fluidized stream of catalyst, transporting catalyst between reaction and regeneration zones, and combusting coke in the regenerator are well known by those skilled in the art of FCC processes. To this end, the art is replete with vessel configurations for contacting catalyst particles with feed and regeneration gas, respectively.
The basic equipment or apparatus for the fluidized catalytic cracking of hydrocarbons has been in existence since the early 1940's. The basic components of the FCC process include a reactor, a regenerator and a catalyst stripper. The reactor includes a contact zone where the hydrocarbon feed is contacted with a particulate catalyst and a separation zone where product vapors from the cracking reaction are separated from the catalyst. Further product separation takes place in a catalyst stripper that receives catalyst from the separation zone and removes entrained hydrocarbons from the catalyst by counter-current contact with steam or another stripping medium. The FCC process is carried out by contacting the starting material whether it be vacuum gas oil, reduced crude, or another source of relatively high boiling hydrocarbons with a catalyst made up of a finely divided or particulate solid material. The catalyst is transported like a fluid by passing gas or vapor through it at sufficient velocity to produce a desired regime of fluid transport. Contact of the oil with the fluidized material catalyzes the cracking reaction. During the cracking reaction, coke will be deposited on the catalyst. Coke is comprised of hydrogen and carbon and can include other materials in trace quantities such as sulfur and metals that enter the process with the starting material. Coke interferes with the catalytic activity of the catalyst by blocking active sites on the catalyst surface where the cracking reactions take place. Catalyst is traditionally transferred from the stripper to a regenerator for purposes of removing the coke by oxidation with an oxygen-containing gas. An inventory of catalyst having a reduced coke content, relative to the catalyst in the stripper, hereinafter referred to as regenerated catalyst, is collected for return to the reaction zone. Oxidizing the coke from the catalyst surface releases a large amount of heat, a portion of which escapes the regenerator with gaseous products of coke oxidation generally referred to as flue gas. The balance of the heat leaves the regenerator with the regenerated catalyst. The fluidized catalyst is continuously circulated from the reaction zone to the regeneration zone and then again to the reaction zone. The fluidized catalyst, as well as providing a catalyst function, acts as a vehicle for the transfer of heat from zone to zone. Catalyst exiting the reaction zone is spoken of as being spent, i.e., partially deactivated by the deposition of coke upon the catalyst.
One improvement to FCC units is the practice of riser cracking. In riser cracking, regenerated catalyst and starting materials enter a pipe reactor and are transported upward by the expansion of the gases that result from the vaporization of the hydrocarbons, and other fluidizing mediums if present upon contact with the hot catalyst. Riser cracking provides good initial catalyst and oil contact and also allows the time of contact between the catalyst and oil to be more closely controlled by eliminating turbulence and backmixing that can vary the catalyst residence time. An average riser cracking zone today will have a catalyst to oil contact time of 1 to 5 seconds. A number of riser designs use a lift gas as a further means of providing a uniform catalyst flow. Lift gas is used to accelerate catalyst in a first section of the riser before introduction of the feed and thereby reduces the turbulence which can vary the contact time between the catalyst and hydrocarbons.
The benefits of using lift gas to pre-accelerate and condition regenerated catalyst in a riser type conversion zone are well known. Lift gas typically has a low concentration of heavy hydrocarbons, i.e. hydrocarbons having a molecular weight of C.sub.3 or greater are avoided. In particular, highly reactive type species such as C.sub.3 plus olefins are unsuitable for lift gas. Thus, lift gas streams comprising steam and light, saturated hydrocarbons are generally used.
The hydrocarbon product of the FCC reaction is recovered in vapor form and transferred to product recovery facilities. These facilities normally comprise a main column for cooling the hydrocarbon vapor from the reactor and recovering a series of heavy cracked products which usually include bottom materials, cycle oil, and heavy gasoline. Lighter materials from the main column enter a gas concentration section for further separation into additional product streams.
Almost all FCC feedstocks will contain some sulfur. This sulfur is typically in the form of organic sulfur compound. During cracking, contact of the feed with the cracking catalyst will convert the feed sulfur to hydrogen sulfide, carbon oxysulfide, normally liquid organic sulfur compounds and residual sulfur that is contained in the coke deposits that form on the catalyst. Although a substantial amount of he sulfur is removed with the vapor product stream from the reactor, a substantial amount of the feed sulfur passes with the catalyst into the regenerator. As coke is burned off the catalyst in the regeneration zone most of the sulfur present on the catalyst is converted to sulfur dioxide with a small amount being converted to sulfur trioxide. The sulfur oxide containing gases are withdrawn from the regenerator with the regenerator flue gases.
An increasing awareness of the health and environmental problems caused by sulfur pollution has led to restrictions on the emissions of sulfur oxides into the atmosphere. Therefore economical methods of reducing sulfur emissions from FCC process units are in demand. One common method of reducing sulfur emissions is to recover sulfur oxides from the flue gas by means of wet gas scrubbing. The high temperature and relatively large volume of the flue gas complicates the direct removal of sulfur oxides and increases the cost of such removal methods. Sulfur oxide emissions from flue gas can also be reduced indirectly by feed treatment to lower the amount of feed sulfur or the use of acceptor or transfer function catalysts that inhibit the formation of sulfur oxides during the combustion of coke in the regenerator. However the removal of sulfur from the feed adds equipment and operational expense to the unit and the use of special catalysts can increase costs and affect the operation of the process.